H-passivated Si Surface Research Articles

Co on the H-passivated Si(001) surface: Density-functional calculations

We have presented an atomic and electronic structures, as well as chemical bonding of Co on the bare, partially H-passivated, and fully H-passivated Si(001)-(2×2) surface using density functional theory. There have been considered three different sites for Co on the surface; (1) an l-site (Co bonded to the lower lying Si-dimer component), (2) an h-site (Co bonded to the higher lying Si-dimer component), and (3) an i-site (intrarow position between adjacent Si dimer rows). The calculations indicate that for the i-site, the Co atom is located at nearly the same height as the Si dimers towards the vicinal region on the bare and partially H-passivated Si(001) surface. For all the remaining cases studied here, the Co atom prefers to stay at the subsurface site.

Hexacene generated on passivated silicon.

On-surface synthesis represents a successful strategy to obtain designed molecular structures on an ultra-clean metal substrate. While metal surfaces are known to favor adsorption, diffusion, and chemical bonding between molecular groups, on-surface synthesis on non-metallic substrates would allow the electrical decoupling of the resulting molecule from the surface, favoring application to electronics and spintronics. Here, we demonstrate the on-surface generation of hexacene by surface-assisted reduction on a H-passivated Si(001) surface. The reaction, observed by scanning tunneling microscopy and spectroscopy, is probably driven by the formation of Si-O complexes at dangling bond defects. Supported by density functional theory calculations, we investigate the interaction of hexacene with the passivated silicon surface, and with single silicon dangling bonds.

Semiconducting Graphene on Silicon from First-Principles Calculations.

Graphene is a semimetal with zero band gap, which makes it impossible to turn electric conduction off below a certain limit. Transformation of graphene into a semiconductor has attracted wide attention. Owing to compatibility with Si technology, graphene adsorbed on a Si substrate is particularly attractive for future applications. However, to date there is little theoretical work on band gap engineering in graphene and its integration with Si technology. Employing first-principles calculations, we study the electronic properties of monolayer and bilayer graphene adsorbed on clean and hydrogen (H)-passivated Si (111)/Si (100) surfaces. Our calculation shows that the interaction between monolayer graphene and a H-passivated Si surface is weak, with the band gap remaining negligible. For bilayer graphene adsorbed onto a H-passivated Si surface, the band gap opens up to 108 meV owing to asymmetry introduction. In contrast, the interaction between graphene and a clean Si surface is strong, leading to formation of chemical bonds and a large band gap of 272 meV. Our results provide guidance for device designs based on integrating graphene with Si technology.

Contact effects and quantum interference in engineered dangling bond loops on silicon surfaces.

Dangling bond structures created on H-passivated silicon surfaces offer a novel platform for engineering planar nanoscale circuits, compatible with conventional semiconductor technologies. In this investigation we focus on the electronic structure and quantum transport signatures of dangling bond loops built on H-passivated Si(100) surfaces contacted by carbon nanoribbons, thus leading to a two-terminal planar, nanoscale setup. The computational studies were carried out to rationalize the influence of the local atomic-scale contacts of the dangling bond system to the mesoscopic electrodes as well as the possibility of revealing quantum interference effects in the dangling bond loops. Our results reveal a strong sensitivity of the low-energy quantum transmission to the loop topology and to the atomistic details of the electrode-loop contact. Varying the length of the loop or the spatial position of at least one of the electrodes has a drastic impact on the quantum interference pattern; depending on whether constructive or destructive interference within the loop takes place, the conductance of the system can be tuned over several orders of magnitude, thus suggesting the possibility of exploiting such quantum mechanical effects in the design of two-dimensional, atomic-scale electronic devices such as logic gates.

Spin transport in dangling-bond wires on doped H-passivated Si(100)

New advances in single-atom manipulation are leading to the creation of atomic structures on H-passivated Si surfaces with functionalities important for the development of atomic and molecular based technologies. We perform total-energy and electron-transport calculations to reveal the properties and understand the features of atomic wires crafted by H removal from the surface. The presence of dopants radically change the wire properties. Our calculations show that dopants have a tendency to approach the dangling-bond wires, and in these conditions, transport is enhanced and spin selective. These results have important implications in the development of atomic-scale spintronics showing that boron, and to a lesser extent phosphorous, convert the wires in high-quality spin filters.

Effect of Molecule–Surface Reaction Mechanism on the Electronic Characteristics and Photovoltaic Performance of Molecularly Modified Si

We report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors.

Experimental and theoretical study of electronic structure of lutetium bi-phthalocyanine

Using Near Edge X-Ray Absorption Fine Structure (NEXAFS) Spectroscopy, the thickness dependent formation of Lutetium Phthalocyanine (LuPc2) films on a stepped passivated Si(100)2×1 reconstructed surface was studied. Density functional theory (DFT) calculations were employed to gain detailed insights into the electronic structure. Photoelectron spectroscopy measurements have not revealed any noticeable interaction of LuPc2 with the H-passivated Si surface. The presented study can be considered to give a comprehensive description of the LuPc2 molecular electronic structure. The DFT calculations reveal the interaction of the two molecular rings with each other and with the metallic center forming new kinds of orbitals in between the phthalocyanine rings, which allows to better understand the experimentally obtained NEXAFS results.

Method for Fabricating Micro/Nanostructures via Scanning Probe Microscope and Anisotropic Wet Etching

The direct modification of silicon, other semiconductors and metal surfaces by the process of local anodic oxidation via electric field from scanning probe microscope (SPM) in conjunction with the absorbed water in atmosphere as the electrolyte is a promising method for fabricating micro/nanostructures. We demonstrated that the process of SPM oxidation and anisotropic wet chemical etching is a low cost and reliable method to produce smooth and uniform etched structures on silicon substrates. Using silicon oxide nanopatterns produced on H-passivated (110) Si surfaces as etching masks, and due to the large (110)/(111) anisotropic ratio of etching rate and the large Si/SiO2 etching selectivity at a relatively low etching temperature and an optimal concentration of aqueous KOH etchant, high-aspect-ratio grating structures have been fabricated by anisotropic wet etching. The approach of combining scanning probe lithography (SPL) with etching technique provides an alternative lithography route to fabricate functional nanophotonic or nanoelectronic devices.

Surface-State Engineering for Interconnects on H-Passivated Si(100)

Surface-state engineering strategies for atomic-size interconnects on H-passivated Si(100) surfaces are explored. The well-known simple interconnect formed by removing H-atoms from one of the Si atoms per dimer of a dimer row along the Si(100) surface is poorly conducting. This is because one-dimensional-like instabilities open electronic gaps. Here, we explore two strategies to reduce the instabilities: spacing the dangling bonds with H atoms and changing the geometry by increasing the lateral size of the wires. The resulting wires are evaluated using density functional theory. Surprisingly, zigzag dangling-bond wires attain atomically confined conduction properties comparable with the conduction of free-standing metallic monatomic wires. These results hint at band-engineering strategies for the development of electronically driven nanocircuits.

Fractal pattern formation in thermal grooving at grain boundaries in Ag films on Si(111) surfaces

Growth of Ag films on Br- and H-passivated Si(111) surfaces and the annealing behaviour have been investigated by Rutherford backscattering spectrometry, scanning electron microscopy and photoemission electron microscopy techniques. Upon annealing the phenomenon of thermal grooving was observed in the Ag films. Depending on the annealing temperature, at an intermediate annealing time Ag depletion (evaporation) from the grain boundaries produces fractal patterns of Ag-depleted regions. Continued annealing eventually produces a percolated network of Ag-depleted regions (thermal grooves) along the grain boundaries and isolated Ag grains appear as the depth of the grooves reaches the substrate. For the fractal structures produced by thermal grooving, the fractal dimension has been estimated to be 1.60±0.04. Observation of a fractal pattern in thermal grooving was not hitherto reported. A thorough analysis of the experimental results has been carried out in the context of current theories. These theories are inadequate to describe the experimental results.

Inducing Electronic Changes in Graphene through Silicon (100) Substrate Modification

We have performed scanning tunneling microscopy and spectroscopy (STM/STS) measurements as well as ab initio calculations for graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces. In order to experimentally study the same graphene piece on both substrates, we develop a method to depassivate hydrogen from under graphene monolayers on the Si(100)/H surface. Our work represents the first demonstration of successful and reproducible depassivation of hydrogen from beneath monolayer graphene flakes on Si(100)/H by electron-stimulated desorption. Ab initio simulations combined with STS taken before and after hydrogen desorption demonstrate that graphene interacts differently with the clean and H-passivated Si(100) surfaces. The Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer. The local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.

Directionality of ο-Phthalaldehyde adsorbed onto H-passivated Si(100) Surface Characterized by NEXAFS and HRPES

The electronic and adsorption structure of o-phthalaldehyde (OPA) on the H-Si(100) surface was investigated by using Near Edge X-ray Fine Structure (NEXAFS) and high resolution photoemission spectroscopy (HRPES). We confirmed that the OPA grown on the H-Si(100) surface showed good dependency with about 60 degree tilting angle using NEXAFS and a single O 1s peak by using HRPES. Hydrogen atom passivated on the Si(100) surface was found to be a seed for making one dimensional organic line that uses a chain reaction as the H-Si(100) surface was compared with the hydrogen free Si(100) surface.

Evolution of Interdiffused Gaussian-Shape Nanolayer in Au-Si(111) System at Ambient Condition

Evolution of interdiffused Gaussian-shape nanolayer of Au-Si, formed due to diffusion of Au into Si(111) substrate at ambient conditions, depends strongly on the Si surface pretreatment/passivation conditions. Negligible diffusion in the Au-OSi(111) sample, confirms the strong barrier action of the oxide-layer against diffusion, while large diffusion in the Au-HSi(111) sample compared to that in the Au-BrSi(111) sample suggests that the H-passivated Si(111) surface is more stable. This nature of the Au-Si(111) system is qualitatively similar to that of the Au-Si(001) system but it differs quantitatively. The size, electronegativity and bond-energy of the passivating elements and the number of dangling bonds on the Si surface influence the instability of the Si surface. This instability, parameterized by growth-time of oxide layer alone, can be utilized to tune the amount of diffusion into the sub-surface Si region. The distribution of growth-time and fractional passivated area, which are related to the improper Si surface passivation, are against such control and needs perfection.

Electronic structure of Bi lines on clean and H-passivated Si(100)

By means of scanning tunnelling microscopy and spectroscopy, we have investigated theelectronic structure of Bi nanolines on clean and H-passivated Si(100) surfaces. Maps of thelocal density of states (LDOS) images of the Bi nanolines are presented for the first time.The spectra obtained for nanolines on a clean Si surface and the LDOS imagesagree with ab initio predicted spectra for the Haiku structure. For nanolines ona H-passivated surface, the spectra obtained suggest that the Bi nanoline maylocally pin the surface Fermi level, and the LDOS images taken at low bias show adistribution of states different to what was expected at the Bi nanolines. The results arediscussed with respect to use of the nanolines as atomic wire interconnections.

Erratum:Ab initiostudy of subsurface diffusion of Cu on the H-passivated Si(001) surface [Phys. Rev. B80, 155426 (2009)

Erratum:<i>Ab initio</i>study of subsurface diffusion of Cu on the H-passivated Si(001) surface [Phys. Rev. B<b>80</b>, 155426 (2009)

Interaction of Ag with the Si(1 1 1)1 × 1–H surface

Synchrotron radiation based photoemission spectroscopy (SRPES) and low energy electron diffraction (LEED) are used to study the interaction between Ag atoms and the Si(1 1 1)1 × 1–H surface. At an Ag coverage of 0.063 monolayers (ML) on the Si(1 1 1)1 × 1–H surface, the Si 2p component corresponding to Si–H bonds decreases, and an additional Si 2p component appears which shifts to a lower binding energy by 109 meV with respect to the Si bulk peak. The new Si 2p component is also observed for 0.25 ML Ag on the Si(1 1 1)7 × 7 surface. These findings suggest that Ag atoms replace the H atoms of the Si(1 1 1)1 × 1–H surface and form direct Ag–Si bonds. Contrary to the widely accepted view that there is no chemical interaction between Ag particles and the H-passivated Si surface, these results are in good agreement with recent first-principles calculations.

Ab initiostudy of subsurface diffusion of Cu on the H-passivated Si(001) surface

In this paper we use density-functional theory calculations to analyze both the stability and diffusion of Cu adatoms near and on the H-passivated Si(001) surface. Two different Cu sources are considered: depositing Cu from vacuum, and contaminating Cu outdiffusing from bulk Si. Deposited Cu from vacuum quickly moves subsurface to an interstitial site in the third Si layer (T2). Once there, Cu adatoms enter a subsurface zigzag migration route between T2 and another subsurface site, $\text{T}2\ensuremath{\rightarrow}\text{HSL}\ensuremath{\rightarrow}\text{T}2$, along the dimer row direction. Contaminating Cu outdiffusing from bulk is found to be a fast diffuser along both parallel and perpendicular directions to the dimer row when far from the surface. It is attracted to the layers close to the surface and becomes trapped at an interstitial site located at the sixth Si layer (T3). As the outdiffusing Cu atoms get closer to the surface, a channeling zigzag diffusion along the dimer row direction, similar to that one followed by deposited Cu from vacuum, is favoured over diffusion along the perpendicular direction. These results are consistent with previous experimental work done on similar systems and will motivate further experiments on the interesting interaction between Cu and Si surfaces.

Growth of oriented crystalline Ag nanoislands on air-exposed Si(0 0 1) surfaces

Growth of Ag islands under ultrahigh vacuum condition on air-exposed Si(0 0 1)-(2 × 1) surfaces has been investigated by in-situ reflection high energy electron diffraction (RHEED). A thin oxide is formed on Si via exposure of the clean Si(0 0 1)-(2 × 1) surface to air. Deposition of Ag on this oxidized surface was carried out at different substrate temperatures. Deposition at room temperature leads to the growth of randomly oriented Ag islands while well-oriented Ag islands, with (0 0 1) Ag||(0 0 1) Si, [1 1 0] Ag||[1 1 0] Si, have been found to grow at substrate temperatures of ≥350 °C in spite of the presence of the oxide layer between Ag islands and Si. The RHEED patterns show similarities with the case of Ag deposition on H-passivated Si(0 0 1) surfaces.

Time-evolution growth of Ag nanolayers on differently-passivated Si(001) surfaces

The growth and evolution of Ag nanolayers on differently-passivated Si(001) substrates at ambient condition have been studied. Initial compactness and smoothness of Ag nanolayer on the H-passivated Si(001) surface are found better compared to those on the Br-passivated Si(001) surface, which can be understood considering surface free energy and surface mobility of the passivated surfaces. As the time passes, the growth of dewetted three-dimensional (3D) islandlike structures (Volmer-Weber-type mode) from comparatively wetted Ag nanolayer (Stranski-Krastanov-type mode) is evident at ambient conditions. Such evolution of growth is through dewetting (related to the change in the interfacial energy due to the oxide growth), migration, and coalesce of Ag, which can even produce large epitaxial [Ag(001)/Si(001)] 3D islands on H-passivated Si(001) surface. The growth rate, size, number density, and epitaxy/nonepitaxy of 3D islands are different for different passivated surfaces. These differences can be realized considering the growth time of oxide (i.e., instability of passivated surface), in-plane inhomogeneity of interfacial energy (i.e., inhomogeneous nature of passivation), and in-plane diffusion of Ag on the passivated surfaces.

Nanotribological properties of precision-controlled regular nanotexture on H-passivated Si surface by current-induced local anodic oxidation

Nano-sized textures resulted from localized electrochemical oxidation by using atomic force microscopy (AFM) were fabricated on H-passivated Si surface. In this paper, the fabrication and nanotribological properties of nanotexture by local anodic oxidation (LAO) on H-passivated Si surface are presented. A special attention is paid to find the relation between the size of oxide nanotexture and operational parameters such as tip-sample pulsed bias voltage, pulsewidth, and relative humidity to fabricate oxide nanotexture. The nanotribological properties were investigated by a colloidal probe. The results indicate that the nanotextures exhibited low adhesion and greatly reduced friction force at nanometer scale.